2,2'-methylene-bis(6-phenylphenol) | 78576-58-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: 2,2'-methylene-bis(6-phenylphenol)
• 英文别名: 2,2'-methylenebis(2-phenylphenol)；2,2'-methylenebis(6-phenylphenol)；2-[(2-Hydroxy-3-phenylphenyl)methyl]-6-phenylphenol
• CAS: 78576-58-6
• 化学式: C₂₅H₂₀O₂
• 分子量: 352.433
• InChiKey: BYDYAWCBQHDWFX-UHFFFAOYSA-N

物化性质

• 熔点：
  115-116 °C(Solv: benzene (71-43-2))
• 沸点：
  519.8±45.0 °C(Predicted)
• 密度：
  1.189±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  27
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  五氯化铌 、 2,2'-methylene-bis(6-phenylphenol) 以 苯 为溶剂， 以84%的产率得到[Nb((OC6H3-6-Ph-2)2CH2)Cl3]
  参考文献：
  名称：

  2,2'-亚甲基-双（6-苯基苯氧化物）的第4和5组金属衍生物

  摘要：

  将苯酚2,2'-亚甲基-双（6-苯基苯酚）[（HOC 6 H 3 Ph）2 CH 2 ]（1）（每Ti当量）加到[TiCl 4 ]或[Ti的烃溶液中（OPr i）4 ]导致二聚体产物[Ti {（OC 6 H 3 Ph）2 CH 2 } Cl 2 ] 2（2）和[Ti {（OC 6 H 3 Ph）2 CH 2 }（μ-OPr i）（OPr i）] 2（3）。结构研究表明2（CHCl 3溶剂化物）处于由两个二芳基氧化物配体的一端连接的两个四面体钛中心的固态状态。相反，3包含通过两个桥接的异丙氧基配体直接连接的五个配位的钛原子。用1当量处理[MCl 5 ]（M = Nb，Ta）。的1所导致微溶的三氯化物4和5，其与吡啶反应以形成可溶加合物[M {（OC 6 H ^ 3的pH）2 CH 2 }氯3（PY）]（M = Nb的，6 ; M =钽，7）。化合物6和7是具有在固态（苯溶剂化物）等结构的聚体

  DOI：

  10.1016/s0277-5387(99)00319-8
• 作为产物：
  描述：

  聚合甲醛 、 邻苯基苯酚 以 xylene 为溶剂， 反应 10.0h， 以77%的产率得到2,2'-methylene-bis(6-phenylphenol)
  参考文献：
  名称：

  Uncatalyzed Phenol-Formaldehyde Reactions. A Convenient Synthesis of Substituted 2,2′-Dihydroxydiphenylmethanes

  摘要：

  DOI：

  10.1055/s-1981-29368

文献信息

• The isolation and chemistry of niobium and tantalum dimethylamides containing mono- and di-aryloxide ancillary ligands
  作者：Scott W. Schweiger、Dana L. Tillison、Matt G. Thorn、Phillip E. Fanwick、Ian P. Rothwell

  DOI：10.1039/b101723n

  日期：——

  The salt complex [Me2NH2][Ta(NMe2)2Cl4] 4 has been isolated from the reaction of [Ta2Cl10] with Me2NH and the anion shown to contain mutually cis-dimethylamido ligands. 4 reacts with Me2NH and pyridine to produce the neutral adducts mer,cis-[Ta(NMe2)2Cl3(HNMe2)] 1 (known compound) and [Ta(NMe2)2Cl3(py)] 5. The solid state structure of [Ta(NMe2)2Cl3(py-4Ph)] 7 shows a mer,cis arrangement of Cl and NMe2 groups. The addition of 2,3,5,6-tetraphenyl- or 2,6-di-isopropyl-phenol (2 equiv) to solutions of 1 in benzene was found to produce a mixture of two isomers each containing a residual Ta–NMe2 and Ta–NHMe2 group. These were formulated as [Ta(OAr)2Cl2(NMe2)(NHMe2)] with the coordinated amine trans to the Ta–NMe2 group and aryloxide ligands either mutually cis or trans. The cis isomer was found to thermally convert to the trans form. The trans isomers [M(OAr)2Cl2(NMe2)(NHMe2)] (M = Ta, OAr = 2,3,5,6-tetraphenyl- or 2,6-di-isopropyl-phenoxide; M = Nb, OAr = 2,3,5,6-tetraphenylphenoxide) are obtained in high yield by treatment of the corresponding tri(chlorides) [M(OAr)2Cl3] with excess Me2NH. The isomorphous/isostructural compounds [M(OC6HPh4-2,3,5,6)2Cl2(NMe2)(py)] (M = Nb, Ta) were structurally characterized and shown to contain the pyridine ligand trans to the Ta–NMe2 group with mutually trans aryloxides. Addition of 2,2′-methylenebis(6-phenylphenol) (HOC6H3Ph)2CH2} to 1 resulted in formation of the compound [Ta(OC6H3Ph)2CH2}Cl2(NMe2)(HNMe2)] 15. The solid state structure of 15 shows the nitrogen atoms to be mutually trans with cis aryloxide oxygen atoms. The eight-membered dioxametallacycle ring is puckered with the methylene bridge folded up towards the Ta–NMe2 group. The reaction pathways leading to these products are discussed.

  盐复合物[Me2NH2][Ta(NMe2)2Cl4] 4是通过[Ta2Cl10]与Me2NH反应获得的，阴离子显示出含有互为顺式的二甲基氨基配体。4与Me2NH和吡啶反应生成中性加合物mer,cis-[Ta(NMe2)2Cl3(HNMe2)] 1（已知化合物）和[Ta(NMe2)2Cl3(py)] 5。[Ta(NMe2)2Cl3(py-4Ph)] 7的固态结构显示Cl和NMe2基团呈现mer,cis排列。向1的苯溶液中添加2,3,5,6-四苯基或2,6-二异丙基苯酚（2当量）会生成两种异构体的混合物，每种异构体都包含残余的Ta–NMe2和Ta–NHMe2基团。这些化合物被表征为[Ta(OAr)2Cl2(NMe2)(NHMe2)]，其中配位的胺基与Ta–NMe2基团呈反式排列，芳氧配体则是互为顺式或反式。发现cis异构体能够热转化为trans形式。通过用过量的Me2NH处理相应的三氯化物[M(OAr)2Cl3]，可以高产率得到反式异构体[M(OAr)2Cl2(NMe2)(NHMe2)]（M=Ta，OAr=2,3,5,6-四苯基-或2,6-二异丙基苯氧化物；M=Nb，OAr=2,3,5,6-四苯基苯氧化物）。同构/同构结构化合物[M(OC6HPh4-2,3,5,6)2Cl2(NMe2)(py)]（M=Nb，Ta）经过结构表征，显示吡啶配体与Ta–NMe2基团呈反式排列，芳氧配体互为反式。将2,2′-亚甲基双（6-苯基酚）(HOC6H3Ph)2CH2}添加到1中，最终形成化合物[Ta(OC6H3Ph)2CH2}Cl2(NMe2)(HNMe2)] 15。15的固态结构显示氮原子互为反式，而顺式芳氧的氧原子互为顺式。八元的二氧金属环呈现皱缩，亚甲基桥折叠向Ta–NMe2基团。讨论了通向这些产物的反应路径。
• PHOSPHONITE CONTAINING CATALYSTS FOR HYDROFORMYLATION PROCESSES
  申请人：Liu Yun-Shan

  公开号：US20090171122A1

  公开（公告）日：2009-07-02

  Novel trivalent organophosphonite ligands having the structure of general formula (I): wherein R is an alkyl or aryl group containing 1 to 30 carbon atoms; Ar 1 and Ar 2 are aryl groups containing 4 to 30 carbon atoms; R1 to R6 are H or alkyl or aryl hydrocarbon radicals containing 1 to 40 carbon atoms; and X is a connecting group or a simple chemical bond, were developed and found to be very active for hydroformylation processes for ethylenically unsaturated substrates. Catalyst solutions prepared from these ligands with a Rh metal show an unusual “ligand acceleration effect” for simple alkenes, i.e., the hydroformylation activity increases as the concentration of ligand increases, and are capable of producing linear or branched aldehydes under typical hydroformylation conditions.

  开发了具有一般式(I)结构的新型三价有机磷酸酯配体，其中R是含有1至30个碳原子的烷基或芳基基团；Ar1和Ar2是含有4至30个碳原子的芳基基团；R1至R6是H或含有1至40个碳原子的烷基或芳基烃基团；X是连接基团或简单化学键，发现它们对于乙烯基不饱和底物的氢甲酰化过程非常活跃。使用这些配体与Rh金属制备的催化剂溶液显示出不寻常的“配体加速效应”对于简单烯烃，即随着配体浓度的增加，氢甲酰化活性增加，并且能够在典型的氢甲酰化条件下产生线性或支链醛。
• Optimization of Asymmetric Catalysts Using Achiral Ligands:  Metal Geometry-Induced Ligand Asymmetry
  作者：Timothy J. Davis、Jaume Balsells、Patrick J. Carroll、Patrick J. Walsh

  DOI：10.1021/ol016003d

  日期：2001.7.1

  resolved chiral ligands. In this Letter, we optimize the asymmetric addition of diethylzinc to aldehydes by modification of achiral methylene bis(phenol) ligands. Upon coordination of the substrate, the achiral ligand becomes asymmetric, a concept termed Metal Geometry-Induced Ligand Asymmetry. The enantioselectivity of the catalyst formed from a single resolved ligand and several achiral ligands ranged from

  [反应：见正文]传统上，不对称催化剂是通过修饰拆分的手性配体来优化的。在这封信中，我们通过修饰非手性亚甲基双（苯酚）配体来优化二乙基锌与醛的不对称加成。在底物配位后，非手性配体变得不对称，这一概念称为金属几何诱导的配体不对称。由单个拆分的配体和几个非手性配体形成的催化剂的对映选择性为9％（R）至83％（S）。
• CASIRACHI G.; CASNATI G.; POCHINI A.; PUGLIA G.; UNGARO R.; SARTORI G., SYNTHESIS, 1981, NO 2, 143-146
  作者：CASIRACHI G.、 CASNATI G.、 POCHINI A.、 PUGLIA G.、 UNGARO R.、 SARTORI G.

  DOI：——

  日期：——
• US7872157B2
  申请人：——

  公开号：US7872157B2

  公开（公告）日：2011-01-18